JP2002189275A - Image forming method for silver halide color photosensitive material and image information forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method for a silver halide color photosensitive material free of the increase of fog and the deterioration of developed color density and gradation balance due to a change in processing, excellent in the color tone of a color developing dye and image stability and having improved suitability to desilvering and improved processing stain and to provide an image information forming method using the sensitive material. SOLUTION: In the image forming method in which the silver halide color photosensitive material having a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer is subjected to a color processing procedure to obtain a dye image, the sensitive material contains a compound of the formula Rf-(O-Rf')n-L-Xm and the processing time of a color developing step used in the color processing procedure is 95-120 sec.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an image on a silver halide color photographic light-sensitive material and a method for forming image information using the same, and more particularly, to a halogenated method having improved development processing characteristics and improved photographic performance. The present invention relates to a method for forming an image on a silver color photographic photosensitive material and a method for forming image information using the same.

[0002]

2. Description of the Related Art In recent years, as silver halide color photographic light-sensitive materials (hereinafter, also referred to as light-sensitive materials) are processed at stores, so-called mini-lab stores are rapidly increasing. Is required. Means for achieving rapid processing include increasing the concentration of a color developing agent described in JP-A-4-67038 and JP-A-4-81848.
Attempts have been made to speed up the processing by activating the color developing solution, such as raising the temperature of the processing described in (1). However, the technique described above is to provide a deterioration of color density and gradation balance rise and the photosensitive layer of fog, in any way satisfactory did.

Recently, in Japanese Patent Application Laid-Open No. 2000-284430, compounds represented by the general formulas (1) to (7) described in the same publication have been proposed as new color developing agents. compared to the developing agent, which is known to the oxidant excellent color tone of a colored dye formed by the coupler and the coupling, and it is possible to improve the storage stability of the dye image. However, when the above color developing agents are used, when the processing conditions are slightly changed, the stability of the obtained image density is insufficient. It turned out that the problem became apparent.

On the other hand, in the case of a developing solution in a large-scale developing plant on the market, the characteristics of the developing solution are easily maintained and controlled.
A method of replenishing a developing agent component using a solid processing agent has become widespread, and the complication and load of preparing a replenisher and adjusting the amount of replenisher as in the past have been released. At the same time, the photographic performance of the photosensitive material to be developed has also been stabilized, but from the viewpoint of the gradation reproducibility between different developing laboratories, it cannot be said that it is at a satisfactory level. Is the current situation.

[0005] In a color developing solution for a silver halide color photographic light-sensitive material, a hydroxylamine compound is generally used as a preservative to prevent oxidation of an aromatic primary amine type color developing agent. In recent years, various improvements have been attempted from the viewpoint of the oxidation resistance of the color developing solution, and are excellent in preservation, have little fluctuation in liquid properties such as pH drop and sedimentation, temperature fluctuation, concentration fluctuation, replenisher. Hydroxylamine compounds which have high stability even when the amount is reduced and have little influence on photographic performance have been found, but further improvement is demanded.

In a silver halide color photographic light-sensitive material, a bleaching process, a fixing process, or a bleach-fixing process is performed after the color development process in order to remove unnecessary developed silver and silver halide. Generally, in these steps, an iron chelate complex salt is often used as a silver bleaching agent, and conventionally, a ferric complex salt of ethylenediaminetetraacetic acid has been widely used. However, improvement research has progressed, and it has rapid desilvering properties, excellent color reversibility, and little bleaching fog.
An iron chelate complex salt with little generation of stain and excellent in liquid stability has been found. However, in a downsized developing machine without a washing bath having a small liquid volume,
Film staining is likely to occur in the steps after the color development step, and this tendency is particularly observed when rapid bleaching is performed. Therefore, a means is desired which has a quick desilvering property, is excellent in recoloring properties, has little bleaching fog, generates less stain, and is less likely to cause film contamination even when using an iron chelate complex salt having excellent liquid stability. Have been.

Further, to enhance the development reaction by increasing the pH of the color developing solution, can be or early development reaction, resulting in or caused to increase fog, such as or varying the gradation Have undesired effects,
Means for reducing this effect are being sought.

On the other hand, the inverted-type silver halide color photographic light-sensitive material, in a so-called reversal color film,
Basically, first black and white development, reversal processing, color development,
Bleaching and / or bleach-fixing and fixing are performed. Then, sensitized development processing is often performed. Under such activation processing conditions, particularly, gradation stability in an intermediate density range is strongly required.

The silver halide color photographic light-sensitive material for photography is generally processed in a final processing bath containing an aldehyde compound in order to impart stability to the dye image after the development processing. To reduce the impact on the environment,
It is desired to treat in a final treatment bath substantially free of aldehyde compounds. In addition, as described above, in a small-sized developing machine having a small liquid volume and having no washing bath, film contamination was likely to occur in each step after the color development step. Therefore, there is a demand for an image forming method in which even if the aldehyde compound is removed, the stability of the dye image is high and the film is hardly stained.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has as its object to reduce the occurrence of fogging and the deterioration of the color density and gradation balance with respect to each development processing change, and to provide a color dye. An object of the present invention is to provide a method for forming an image of a silver halide color photographic light-sensitive material which is excellent in color tone and image stability, and has improved desilvering property and processing stain, and an image information forming method using the same.

[0011]

The above object of the present invention has been attained by the following constitutions.

1. On one side of the support, a red-sensitive layer,
A silver halide color photographic material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, which is exposed to light and then subjected to color development to obtain a dye image. At least one layer of the light-sensitive material contains the compound represented by the formula (F), and the processing time of the color development step used in the color development processing is 95 to 120.
Image forming method for a silver halide color photographic light-sensitive material, wherein

2. On one side of the support, a red-sensitive layer,
A silver halide color photographic light-sensitive material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, which is exposed to light and then color-developed to obtain a dye image. At least one layer of the light-sensitive material contains the compound represented by the general formula (F), and the color developing solution used in the color development processing is the general formula (1) to (7).
The image forming method of a silver halide color photographic light-sensitive material characterized by containing a color developing agent at least one selected from the.

3. On one side of the support, a red-sensitive layer,
A silver halide color photographic material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, which is exposed to light and then subjected to color development to obtain a dye image. At least one layer of the light-sensitive material contains the compound represented by the formula (F), and a color developing solution used in the color developing process is replenished from a replenisher prepared with a solid processing agent. For forming an image of a silver halide color photographic light-sensitive material.

4. On one side of the support, a red-sensitive layer,
A silver halide color photographic material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, which is exposed to light and then subjected to color development to obtain a dye image. At least one layer of the light-sensitive material contains the compound represented by the general formula (F), and the color developing solution used in the color development processing contains the compound represented by the general formula (a). A method for forming an image of a silver halide color photographic light-sensitive material.

5. On one side of the support, a red-sensitive layer,
A silver halide color photographic material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, which is exposed to light and then subjected to color development to obtain a dye image. At least one layer of the light-sensitive material contains the compound represented by the general formula (F), and at least one of the bleaching processing solution and the bleach-fixing processing solution used in the color development processing has the general formula (b) to (b). e) a method for forming an image of a silver halide color photographic light-sensitive material, characterized by containing at least one member selected from the group consisting of:

6. On one side of the support, a red-sensitive layer,
A silver halide color photographic material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, which is exposed to light and then subjected to color development to obtain a dye image. Silver halide, wherein at least one layer of the light-sensitive material contains the compound represented by formula (F), and the pH of the color developing solution used in the color developing process is 10.5 or more. An image forming method for a color photographic light-sensitive material.

[7] On one side of the support, a red-sensitive layer,
A silver halide color photographic material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, which is exposed to light and then subjected to color development to obtain a dye image. At least one layer of the light-sensitive material contains the compound represented by the general formula (F), and the color development processing includes at least a first black-and-white development step, a reversal processing step,
An image forming method for a silver halide color photographic light-sensitive material, which is a reversal type color developing process comprising a color developing process, a bleaching process, a fixing process or a bleach-fixing process.

8. On one side of the support, a red-sensitive layer,
A silver halide color photographic material having a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, which is exposed to light and then subjected to color development to obtain a dye image. A silver halide color, wherein at least one layer of the light-sensitive material contains the compound represented by the formula (F), and the final processing bath of the color development processing contains substantially no aldehyde compound. An image forming method for a photographic light-sensitive material.

9. 9. The compound according to any one of items 1 to 8, wherein the compound represented by the formula (F) is contained in the outermost layer of the silver halide color photographic light-sensitive material.
Item.

10. 10. After forming an image by the method according to any one of the above items 1 to 9, the formed image information is read by an image sensor, the image information is converted into electric signal information, and an image is formed by arithmetic processing based on the electric signal information. image information forming method, which comprises the process.

Hereinafter, the present invention will be described in detail. (Fluorine-containing surfactant) In the silver halide color photographic light-sensitive material according to the present invention, the fluorine-containing atom surfactant represented by the above general formula (F) (hereinafter also referred to as a fluorine-containing surfactant) is used. It is characterized by containing.

In the general formula (F), Rf represents an alkyl group, an aryl group or an alkenyl group containing at least one fluorine atom, preferably having 1 to 18 carbon atoms, more preferably 2 to 12 carbon atoms. It is preferable that it is especially 3-7.

Rf 'represents an alkylene group containing at least one fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 2 to 5 carbon atoms, particularly preferably 2 or 3. Is preferred.

Further, (O-Rf ') as the _n, for example _{(O-Rf1') k -} (O-Rf2 ') l ( However, k +
(1 = n), a set of different (O-Rf ′) may be used. n and m are each an integer of 1 or more,
n is preferably 1 or more and 10 or less, and m is preferably 1 or more and 3 or less.

L represents a simple bond or a linking group,
An alkylene group, an arylene group, or a divalent linking group containing a hetero atom is preferable.

X represents a hydroxy group, an anionic group or a cationic group, and the anionic group is preferably, for example, a carboxyl group, a sulfonic acid group, or a phosphate group. As the counter cation, for example, a sodium ion, a potassium ion Preferred are alkali metal ions, ammonium ions and the like. As the cationic group, a quaternary alkylammonium group is preferable, and as the counter anion, for example, a halide ion, a p-toluenesulfonic acid ion, or the like is preferable.

The following are specific examples of preferred fluorine-based surfactants that can be used in the present invention, but the fluorine-based surfactants that can be used in the present invention are not limited to these.

[0029] [anionic Surfactant _{1: C 5 F 11 - (} O-CF 2) -O-PO (ONa) 2 2: HC 6 F 12 - (O-CF 2) -O-PO (ONa _{) 2 3: C 8 F 17} - (O-CF 2) -O-PO (ONa) 2 4: C 10 F 21 - (O-CF 2) -O-PO (ONa) 2 5: C 12 F 25 _{- (O-CF 2) -O} -PO (ONa) 2 6: C 3 F 7 - (O-C 2 F 4) -O-PO (ONa) 2 7: C 4 F 9 - (O-C 2 _{F 4) -O-PO (ONa} ) 2 8: C 5 F 11 - (O-C 2 F 4) -O-PO (ONa) 2 9: HC 6 F 12 - (O-C 2 F 4) - _{O-PO (ONa) 2 10} : C 7 F 15 - (O-C 2 F 4) -O-PO (ONa) 2 11: C 9 F 19 - (O-C 2 F 4) -O-PO ( _{ONa) 2 12: C 11 F} 23 - (O-C 2 F 4) -O-PO (ONa
_{2 13: C 3 F 7 -} (O-CF 2) 6 -O-PO (ONa) 2 14: C 4 F 9 - (O-CF 2) 6 -O-PO (ONa) 2 15: C 5 F _{11 - (O-CF 2)} 5 -O-PO (ONa) 2 16: HC 6 F 12 - (O-CF 2) 3 -O-PO (ON
_{a) 2 17: C 3 F} 7 - [O- (CF _{2) 3]} -COONa 18: C ₄ F ₉ - [O- (CF _{2) 3]} -COONa 19: C ₅ F ₁₁ - [O- ( CF _{2) 3]} -COONa 20: HC ₇ F ₁₄ - [O- (CF _{2) 3]} -O-CH (C
_{OONa) 2 21: C 8 F} 17 - [O- (CF _{2) 3]} -O-CH (CO
_{ONa) 2 22: C 3 F} 7 - [O- (CF _{2) 5]} -COONa 23: C ₄ F ₉ - [O- (CF _{2) 5]} -COONa 24: C ₅ F ₁₁ - [O- ( CF _{2) 5]} -COONa 25: C ₇ F ₁₅ - [O- (CF _{2) 5] -COONa 26: C 3 F 7 -} (O-C 2 F 4) 5 -COONa 27: C 4 F 9 - _{(O-C 2 F 4)} 2 -COONa 28: C 5 F 11 - (O-C 2 F 4) 2 -COONa 29: HC 7 F 14 - (O-C 2 F 4) 2 -COONa 30: C _{9 F 19 - (O-C} 2 F 4) 2 -COONa 31: C 2 F 5 - (O-C 2 F 4) 3 -COONa 32: C 2 F 5 - (O-C 2 F 4) 5 - _{COONa 33: C 3 F 7 -} (O-C 2 F 4) 4 -COONa 34: C 4 F 9 - (O-C 2 F 4) 3 -COONa 35: C 5 F 11 - (O-C 2 F ₄ ) ₃ − NHCOCH (CO
_{ONa) 2 36: HC 6 F} 12 - (O-C 2 F 4) 3 -NHCOCH (C
_{OONa) 2 37: C 4 F} 9 - (O-C 2 F 4) 2 -OCF 2 COONa 38: C 5 F 11 - (O-C 2 F 4) 2 -OCF 2 COONa 39: C 7 F 15 - _{(O-C 2 F 4)} 2 -OCF 2 COONa 40: C 4 F 9 -OCF 2 - [O- (CF _{2) 5]} -COO
_{K 41: C 5 F 11 -OCF} 2 - [O- (CF _{2) 5]} -COO
_{K 42: HC 6 F 12 -OCF} 2 - [O- (CF _{2) 5]} -CO
_{OK 43: C 4 F 9 -} (O-C 2 F 4) 5 - [O- (CF _{2) 3]
-COOK 44: C 5 F 11 -} (O-C 2 F 4) 2 - [O- (CF _{2) 3]
-COOK 45: C 6 F 13 -} (O-C 2 F 4) 2 - [O- (CF _{2) 3]
-COOK 46: C 12 F 25 -} (O-CF 2) -O-SO 3 Na 47: C 7 F 15 - (O-C 2 F 4) -OC 3 H 6 -SO 3 Na 48: C 4 F _{9 - (O-CF 2)} 6 -O-SO 3 Na 49: HC 5 F 10 - (O-CF 2) 5 -OC 3 H 6 -SO 3 N
_{a 50: HC 6 F 12 -} (O-CF 2) 3 -O-SO 3 Na 51: C 5 F 11 - (O-C 2 F 4) 2 -OC 3 H 6 -SO 3 N
_{a 52: C 7 F 15 -} (O-C 2 F 4) 2 -O-SO 3 Na 53: C 3 F 7 - (O-C 2 F 4) 4 -OC 3 H 6 -SO 3 Na 54: _{C 4 F 9 - (O-} C 2 F 4) 3 -O-SO 3 Na 55: HC 5 F 10 - (O-C 2 F 4) 3 -OC 3 H 6 -SO 3
_{Na 56: C 5 F 11 -OCF} 2 - [O- (CF _{2) 5]} -O-S
_{O 3 Na 57: C 4 F} 9 - (O-C 2 F 4) 2 - [O- (CF _{2) 3]
-O-SO 3 Na 58: (} HCF 2) 3 C- (O-C 2 F 4) 3 -O-SO 3 N
_{a 59: (CF 3) 2} CFCF 2 CF 2 - (O-CF 2) 5 -O
_{C 3 H 6 -SO 3 Na 60} : C 11 F 23 - (O-C 2 F 4) -O-SO 3 Na [cationic surfactant] _{61: C 4 F 9 - (} O-C 2 F 4 ) ₃ -NHCO- (CH ₂ )
^{_{3 -N + (CH 3) 3}} , Br - 62: C 5 F 11 - (O-C 2 F 4) 2 -NHCO- (C
^{_{H 2) 3 -N + (CH}} 3) 3, Br - 63: HC 6 F 12 - (O-C 2 F 4) 2 -NHCO- (CH
^{_{2) 3 -N + (CH 3}} ) 3, Br - 64: C 4 F 9 - (O-C 2 F 4) 3 -O-CH 2 -N + (C
_{H 3) 2 (C 2 H} 4 OH), Br - 65: C 5 F 11 - (O-C 2 F 4) 2 -O-CH 2 -N + (C
_{H 3) 2 (C 2 H} 4 OH), Br - 66: HC 6 F 12 - (O-C 2 F 4) 2 -O-CH 2 -N
^{_{+ (CH 3) 2 (C}} 2 H 4 OH), Br - 67: C 5 F 11 -OCF 2 - (O-C 2 F 4) -NHCO-
^{_{(CH 2) 3 -N + (}} CH 3) 3, Br - 68: (CF 3) 3 C- (O-C 2 F 4) 3 -O-CH 2 -N
^{_{+ (CH 3) 2 (C}} 2 H 4 OH), Br - [nonionic Surfactant _{69: C 12 F 25 - (} O-CF 2) -OH 70: C 7 F 15 - (O-C 2 _{F 4) -OH 71: C 4} F 9 - (O-CF 2) 6 -OC 3 H 6 -OH 72: C 5 F 11 - (O-CF 2) 5 -OC 3 H 6 -OH 73: HC _{6 F 12 - (O-CF} 2) 3 -OH 74: C 5 F 11 - (O-C 2 F 4) 2 -OC 3 H 6 -OH 75: C 7 F 15 - (O-C 2 F 4 _{) 2 -OC 3 H 6 -OH 76} : C 3 F 7 - (O-C 2 F 4) 4 -OC 3 H 6 -OH 77: HC 4 F 8 - (O-C 2 F 4) 3 -O -C (C ₂ H ₄ O
_{H) 3 78: C 5 F} 11 - (O-C 2 F 4) 3 -OC 3 H 6 -OH 79: C 5 F 11 -OCF 2 - [O- (CF _{2) 5]} -OH 80: C _{4 F 9 - (O-C} 2 F 4) 2 - [O- (CF _{2) 3]}
—OH 81: (CF ₃ ) ₃ C— (O—C ₂ F ₄ ) ₃ —OH 82: (HCF ₂ ) ₂ CFCF ₂ CF ₂ — (O—CF ₂ ) ₅ —
OH 83: C ₁₁ F ₂₃ - The synthesis method of _{(O-C 2 F 4)} 4 OH The above respective fluorine-based surfactant, that Kohyo No. 10-500950, the Nos. 11-504360 helpful Can be.

The fluorine-based surfactant according to the present invention preferably has a total of 7 or more carbon atoms to which a fluorine atom is bonded, particularly preferably 8 or more and 20 or less.

The content of the fluorinated surfactant in the constituent layers of the light-sensitive material of the present invention is 0.01 to the colloid of the hydrophilic layer.
It is preferably in the range of 範 囲 3% by mass, particularly preferably in the range of 0.02 to 1% by mass. When the content of the fluorine-based surfactant is less than the above range, the effect of the present invention is small, and when the content is more than the above range, the coating solution is easily foamed or easily aggregated. In addition, it is not preferable because it deteriorates the surface of the formed coating film.

The details of each claim of the present invention will be described below. (Invention according to claim 1) In the invention according to claim 1, after the photosensitive material containing the fluorinated surfactant represented by the general formula (F) is exposed to light, the processing time in the color development step is increased. Is performed in the range of 95 to 120 seconds to obtain a dye image.

The processing time of the color development step in the present invention is in the range of 95 seconds to 120 seconds, and more preferably 95 seconds to 105 seconds.

The processing temperature in the color development step of the present invention is not particularly limited, but is preferably in the range of 40 ° C. to 55 ° C., more preferably 40 ° C. to 45 ° C.

As the developing agent and other additives used in the color developing process of the present invention, and a developing machine to be used, known ones can be used.

A photosensitive material containing a fluorine-based surfactant is subjected to color development in a color developing solution for 95 to 120 seconds after image exposure to obtain a dye image. It is possible to perform excellent image formation without increasing fog and deteriorating the color density and gradation balance of each photosensitive layer. That is, the photosensitive material containing a fluorine-containing surfactant according to the present invention, the improvement in developing characteristics even if the rapid processing, improvement in photographic performance is desired.

(Invention according to claim 2) In the invention according to claim 2, after the photosensitive material containing the fluorinated surfactant represented by the general formula (F) is exposed to light, It is characterized in that a dye image is obtained by processing with a color developing solution containing at least one color developing agent selected from (1) to (7). With this configuration, the color tone of the color dye is excellent, and This is to improve the storage stability of the dye image.

[0038] Hereinafter, the general formula (1) to the color developing agent are described in detail represented by (7). In R _{1 to} R ₈ and m of the compound represented by the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represent a hydrogen atom or a substituent. More specifically, R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom or a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, and a hydroxyl group. , Carboxy group, sulfo group, alkoxy group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group A carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic oxy group,
Examples include an azo group, an acyloxy group, a carbamoyloxy group, a silyl group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, and an acyl group. These are alkyl, alkenyl, alkynyl, aryl, hydroxyl, nitro, cyano, halogen or other oxygen, nitrogen,
It may be substituted with a substituent formed by a sulfur atom or a carbon atom.

R ₅ and R ₆ represent a hydrogen atom or a substituent, and the substituent in this case represents an alkyl group, an aryl group or a heterocyclic group. The details are the same as the substituents described for R ₁ , R ₂ , R ₃ and R ₄ . Provided that when R _5, R ₆ is a heterocyclic group, bound to the carbon atom constituting the hetero ring of the heterocyclic group. R ₇ represents an alkyl group. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . R ₈ represents a substituent. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . m represents an integer of 0 to 3.

R in the compound represented by the general formula (2)₉~
R₁₃And n will be described in detail. R₉And R_TenAre the same
And each may represent a hydrogen atom or a substituent.
You. See R₁, R_Two, R_ThreeAnd R_FourAlso explained in
Synonymous with R₁₁And R ₁₂Are the same but different
Each represents a hydrogen atom or a substituent, in which case the substituent
Represents an alkyl group, an aryl group or a heterocyclic group. So
The details of R₁, R_Two, R_ThreeAnd R_FourSame as described in
Righteous. Where R₁₁, R₁₂Is a heterocyclic group,
Bonded to a carbon atom constituting the heterocyclic ring of the heterocyclic group
I have. R₁₃Represents a substituent. See R₁, R_Two, R
_ThreeAnd R_FourIs synonymous with the one described in. n is 0-3
Represents an integer.

R ₁₄ to R ₁₄ in the compound represented by the general formula (3)
It will be described in detail R ₂₂ and p. R _{14 to} R ₂₁ may be the same or different and each represents a hydrogen atom or a substituent. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . R ₂₂ represents a substituent. See R
It has the same meaning as that described for ₁ , R ₂ , R ₃ and R ₄ . p
Represents an integer of 0 to 4.

R ₂₃ in the compound represented by the general formula (4),
R ₂₄ and R ₂₅ will be described in detail. R ₂₃ has 1 to 6 carbon atoms
Represents a straight-chain or branched unsubstituted alkyl group, or a straight-chain or branched hydroxyalkyl group having 2 to 6 carbon atoms in which the main chain has 2 to 6 carbon atoms. Here, the main chain refers to a connecting group between the connecting nitrogen atom and the hydroxyl group,
When R ₂₃ has a plurality of hydroxyl groups, it indicates the one having the least number of carbon atoms. Specific examples of R ₂₃ include methyl, ethyl, n-propyl, isopropyl, n- butyl, sec- butyl, n- hexyl, neopentyl, 3-hydroxy propyl, 2-hydroxyethyl, 2-hydroxypropyl, 4 - hydroxybutyl, 2,3-dihydroxypropyl, 5-hydroxypentyl, 6-hydroxyhexyl, 4-hydroxypentyl, 3-hydroxybutyl, 4-hydroxy-4-methylpentyl, 5,6-dihydroxy-hexyl, 2,
3,4-trihydroxybutyl and the like.

R ₂₄ has 2 carbon atoms whose main chain has 2 to 6 carbon atoms.
Represents a straight-chain or branched unsubstituted alkylene group of 6 to 6, or a straight-chain or branched hydroxylalkylene group of 2 to 6 carbon atoms having a main chain of 2 to 6 carbon atoms. Here, the main chain refers to a connecting chain of the connecting nitrogen atom and the hydroxyl group described in the general formula (4). When R ₂₄ has one or more hydroxyl groups, the main chain is counted from the nitrogen atom side. The hydroxyl group bonded on the carbon atom having the least carbon number corresponds to the hydroxyl group described in the general formula (4), and the connecting chain is the main chain. Specific examples of R ₂₄ are, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1-methyltrimethylene, 2-methylethylene, 3-hydroxymethyl-ethylene, 2-methyltrimethylene, 3-methyltrimethylene , 3-methyl pentamethylene, 2-methylpentamethylene, 2- ethyl trimethylene, 2-methyl pentamethylene, 2-ethyl-trimethylene, etc. 3- (2-hydroxyethyl) trimethylene are exemplified.

R ₂₅ represents a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. Specific examples of R ₂₅ include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, cyclopropyl and the like.

R of the general formula (4)_{twenty three}, R_{twenty four}, R_{twenty five}About
The preferred combinations are described below. R
_{twenty three}Is methyl, ethyl, n-propyl, 2-hydro
Xyethyl group, 3-hydroxypropyl group, 4-hydro
A xybutyl group;_{twenty four}Has a main chain of 2 to 4 carbon atoms
Is an alkylene group having 2 to 5 carbon atoms of_{twenty five}Is methyl
And the combination of an ethyl group is preferred. More preferred
A good combination is R _{twenty three}Is a methyl group, an ethyl group, n
-Propyl group, 2-hydroxyethyl group, 3-hydroxy
A cypropyl group or a 4-hydroxybutyl group;_{twenty four}Is
The main chain is an unsubstituted C 2-4 alkyl group having 2-4 carbon atoms.
A kylene group;_{twenty five}Is preferably a methyl group
Good.

R ₂₆ in the compound represented by the general formula (5),
R ₂₇ , R ₂₈ and R ₂₉ will be described in detail. R ₂₆ represents a linear or branched alkyl group having 1 to 6 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methanesulfonamidoethyl,
Methanesulfonamide propyl, 2-methanesulfonyl-ethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2,3-dihydroxypropyl, 3,4-dihydroxy Butyl, n
- hexyl, 5-hydroxypentyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoyl-aminoethyl, 3-carbamoyl-aminopropyl, 4-carbamoylamino-butyl, 4-sulfobutyl, 4-carbamoylbutyl, 2-carbamoyl 1- Methylethyl,
4-nitrobutyl can be mentioned.

R ₂₇ represents a straight-chain or branched alkylene group having 2 to 6 carbon atoms in which the main chain has 2 to 6 carbon atoms. R ₂₇
As specific examples of, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1-
Methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, 3-methylpentamethylene, 2-methylpentamethylene, 2-ethyltrimethylene, 2-methylpentamethylene, 2-ethyltrimethylene,
(2-hydroxyethyl) trimethylene are exemplified.

[0048] R ₂₈ represents a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples of R ₂₈ include, for example, methyl,
Ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl and the like.

R ₂₉ represents a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. Specific examples of R ₂₉ include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, cyclopropyl and the like.

In the general formula (5), R ₂₆ , R ₂₇ , R ₂₈ ,
For R ₂₉ described for the preferred combinations below. R ₂₆ is a methyl group, an ethyl group or an n-propyl group, R ₂₇ is a C 3-4 alkylene group having a main chain of 3-4 carbon atoms, R ₂₈ is a methyl group or an ethyl group, combinations R ₂₉ is a methyl group. As a more preferable combination, a combination in which R ₂₆ is a methyl group or an ethyl group, R ₂₇ is a trimethylene group or a tetramethylene group, R ₂₈ is a methyl group, and R ₂₉ is a methyl group is preferable.

The compound represented by formula (6) will be described in detail. R ₃₀ is an alkyl group, and more preferably, R ₃₀ is a linear or branched alkyl group having 1 to 6 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or a cycloalkenyl group; such as hydroxyl group, a nitro group, a carboxyl group, a cyano group, a halogen atom, a nitrogen atom, may be substituted with a substituent such as linking a sulfur atom or a carbonyl group, among these, preferred R ₃₀ As methyl, ethyl, propyl, isopropyl, t-butyl,
2-hydroxyethyl, 3-hydroxypropyl, 2-
Methoxyethyl, 2-methanesulfonamidoethyl, 2
An acetamidoethyl group, more preferably a methyl, ethyl, propyl or isopropyl group.

R ₃₁ is an alkylene group having a main chain of 2 or more carbon atoms, more preferably R ₃₁ is a straight-chain or branched alkylene group, which is a substituent such as a hydroxyl group,
A nitro group, a carboxyl group, a cyano group, a halogen atom or another oxygen atom, a nitrogen atom, a sulfur atom or a substituent linked by a carbonyl group or the like may be substituted. Of these, preferred R ₃₁ is a main chain. An alkylene group having 2 to 5 carbon atoms, for example, an ethylene, propylene, butylene, 2-methylpropylene, or 2-methylethylene group.

R ₃₂ and R ₃₃ are a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R ₃₂ and R ₃₃ may be the same or different. More preferably, the alkyl group having 4 or less carbon atoms represented by R ₃₂ and R ₃₃ is a linear or branched alkyl group, and these are substituents such as a hydroxyl group, a nitro group, a carboxyl group, a cyano group, a halogen atom or other An oxygen atom, a nitrogen atom, a sulfur atom or a substituent linked by a carbonyl group or the like may be substituted, and among these, preferred R ₃₂ and R ₃₃ are a hydrogen atom, methyl,
An ethyl group, more preferably a hydrogen atom.

[0054] R ₃₄ is an alkyl group, a substituted group linked via an halogen atom or a nitrogen or oxygen atom, is more specifically R ₃₄ is an alkyl group (preferably 1 to 16 carbon atoms
A straight-chain or branched alkyl group), an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group and a cycloalkenyl group. Of these substituents, preferred R ₃₄ is an alkyl group, an alkoxy group, an alkoxycarbonylamino group , A ureido group, more preferably an alkyl group, and among them, a methyl group and an ethyl group are particularly preferable.

Q represents an integer of 0 to 4. when q is 2 or more, R ₃₄ may be the same or different. Preferred q is 0 or 1, and more preferably q is 1.

The compound represented by formula (7) will be described in detail. R ₃₈ is a substituent, and more specifically, R ₃₈
Is a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, nitro group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino Group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group , An aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, and an acyl group.

Among these substituents, R ₃₈ is preferably an alkyl group, an alkoxy group, an alkoxycarbonylamino group, or a ureido group, more preferably an alkyl group, and particularly preferably a methyl group or an ethyl group. r is represented by an integer of 0 to 4. When r is 2 or more, R ₃₈
May be the same or different. Desirable r is 0 or 1, and more preferably r is 1.

R ₃₅ is an alkyl group.
₃₅ is an alkyl group (a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms) which is an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other oxygen atoms, nitrogen, Atom, a sulfur atom or a carbon atom, which may be substituted with a substituent, and among these substituents, preferred R ₃₅ is methyl, ethyl, propyl, isopropyl, t-butyl,
2-hydroxyethyl, 3-hydroxypropyl, 2-
Methoxyethyl, 2-methanesulfonamidoethyl, 2
-Acetamidoethyl, 4-hydroxybutyl group, more preferably methyl, ethyl, propyl, isopropyl, t-butyl group, among which methyl, ethyl,
A propyl group is particularly preferred, and an ethyl group and a propyl group are most preferred.

R ₃₆ is an alkylene group. More specifically, R ₃₆ is an alkylene group having a main chain of 2 or more carbon atoms (linear or branched alkylene group), which is a hydroxyl group, a nitro group, a cyano group, a halogen atom. Or other substituents linked by an oxygen atom, a nitrogen atom, a sulfur atom, or a carbon atom. Of these substituents, preferred R
₃₆ is an ethylene, 2-methylethylene, trimethylene, tetramethylene, 2-methyltrimethylene or 1-methylethylene group, with ethylene, trimethylene and tetramethylene being particularly preferred.

R ₃₇ is a hydrogen atom or an alkyl group. More specifically, R ₃₇ is a hydrogen atom or an alkyl group (having 1 to 1 carbon atoms).
16 straight-chain or branched alkyl groups) which are linked by alkenyl, alkynyl, aryl, hydroxyl, nitro, carboxyl, cyano, halogen or other oxygen, nitrogen, sulfur or carbon atoms May be substituted with, among these,
Preferred R ₃₇ is a hydrogen atom, a methyl or ethyl group, and more preferably a hydrogen atom. X is -CO-NR
_{39 (R 41), - CO} -OR 40, -SO 2 -NR
₃₉ is a group selected from the group consisting of (R ₄₁ ),
NR ₃₉ (R ₄₁ ) and —SO ₂ —NR ₃₉ (R ₄₁ ) are preferred.

[0061] R ₃₉ and R ₄₁ are a hydrogen atom, an alkyl group and an aryl group and more particularly R ₃₉ and R ₄₁ are hydrogen atoms in these alkyl group (linear or branched alkyl group having 1 to 16 carbon atoms) Alkenyl group, alkynyl group, aryl group, hydroxyl group, nitro group, carboxyl group, cyano group, halogen atom or other oxygen atom, nitrogen atom,
R ₃₉ may be substituted with a substituent linked by a sulfur atom or a carbon atom. Of these, preferred R ₃₉ is a hydrogen atom or an alkyl group, and among the alkyl groups, a methyl group and an ethyl group are preferred. Among them, preferred R ₃₉ is a hydrogen atom. The preferred R ₄₁ is preferably a hydrogen atom or an alkyl group in R ₄₁ where X is _{-CO-NR 39 (R 41)} ,
Hydrogen atoms are particularly preferred. X is -SO ₂ -NR
_{In the case of 39} (R ₄₁ ), R ₄₁ is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and particularly preferably a methyl group or an ethyl group.

R ₄₀ is an alkyl group or an aryl group. More specifically, R ₄₀ is an alkyl group (a linear or branched alkyl group having 1 to 16 carbon atoms), which is a hydroxyl group, a nitro group, a carboxyl group, a cyano group, It may be substituted by a halogen atom or another substituent linked by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom, and among them, preferred R ₄₀ is an alkyl group, and among them, a methyl group and an ethyl group are particularly preferred.

The typical examples of the compounds represented by formulas (1) to (7) are shown below.

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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The color developing agents represented by the general formulas (1) to (7) are usually used in an amount of 1 g to 100 g per liter of the color developing solution.
g from the viewpoint of rapid processing and solubility of the active ingredient, from 3 g to 1 g of the color developing solution.
It is preferably 50 g, more preferably 4.5 g to 50 g, and particularly preferably 6.0 g to 50 g.

The color developing solution may contain the following developing solution components in addition to the above components. As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium carbonate, potassium carbonate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc., alone or in combination Can be used. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borate are used for the purpose of preparation or for the purpose of increasing ionic strength. be able to.

If necessary, inorganic and organic antifoggants may be added. Examples of these antifoggants include sodium bromide, potassium bromide, sodium iodide and potassium iodide. Starting from inorganic halide compounds, 6-nitrobenzimidazole described in U.S. Pat. No. 2,496,940, 5-nitrobenzimidazole described in 2,497,917 and 2,656,271, and Other examples include o-phenylenediamine, mercaptobenzimidazole, mercaptobenzoxazole, thiouracil, 5-methylbenzotriazole, and heterocyclic compounds described in JP-B-46-41675.

In addition to these various components, JP-B-46-1
No. 9039, the same 45-6149, U.S. Patent No. 3,29
The development inhibitor compounds disclosed in US Pat. No. 5,976 can be used.

Of the above antifoggants, bromide ions supplied from sodium bromide, potassium bromide, etc. are preferably at most 1.3 × 10 ^-2 mol / L, more preferably from the viewpoint of rapid treatment. Is 8.4 × 10 ⁻³ mol / L or less.

[0082] Also, it is possible to use also a development accelerator, if necessary. U.S. Pat. No. 2,648,
No. 604, No. 3,671, 247, JP-B-44-9
No. 503, various kinds of pyridinium compounds, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, US Pat. Nos. 2,533,990 and 2,531 No. 2,832, No. 2,950,970, No. 2,577,127,
And nonionic compounds such as polyethylene glycol and derivatives thereof and polythioethers described in JP-B-44-9504, organic solvents and organic amines, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like described in JP-B-44-9509. included. Also, benzyl alcohol, phenethyl alcohol described in U.S. Pat. No. 2,304,925, and others,
Examples include acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like.

Further, the color developer contains various phosphoric acids such as sodium tetrapolyphosphate, tetrasodium pyrophosphate, condensed phosphate and salts thereof, and various chelating agents as a water softener or a heavy metal sequestering agent. can.

Further, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, .beta.-cyclodextrin, and other such color developing solutions may be used in the color developing solution as disclosed in JP-B-47-33378 and JP-B-44-950.
The compounds described in No. 9 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexalfate (methol), phenidone, N, N'-diethyl-p
-Aminophenol hydrochloride, N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the amount of addition is usually 0.01 g to 1.0 g.
/ L is preferred. In addition, if necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (a so-called DIR coupler), a development inhibitor releasing compound, or the like can be added.

Further, other various additives such as a stain inhibitor, an anti-sludge agent and a layering effect promoter can be used.

Each component of the above color developing solution can be prepared by sequentially adding to a certain amount of water and stirring. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a concentrated aqueous solution of a plurality of components each of which can coexist stably, or a solution prepared in advance in a small container in a solid state is added to water and stirred to prepare a color developing solution. it can.

In the present invention, the color developing solution is adjusted to pH
It can be used in any pH range from 9.5 to 14, but generally at a low pH, the color development reaction is not sufficient, and at a high pH, various side reactions of the color developing agent occur.
It is preferred to use between 3.

(Invention according to claim 3) In the invention according to claim 3, after the photosensitive material containing the fluorine-containing surfactant represented by the general formula (F) is exposed, the solid processing agent It is characterized by processing with a color developing solution replenished by the above method, whereby the gradation stability can be improved. In the color developing process according to the third aspect, the solid processing agent is substantially directly charged into the processing tank of the automatic developing machine.

The solid processing agents used in the present invention include powder processing agents, solid processing agents such as tablets, pills, and granules, which have been subjected to a moisture-proof treatment as required. Those having a shape which is regulated with the danger of transportation are not included in the solid processing agent according to the present invention.

The powder as used in the present invention means an aggregate of fine crystals. The granules referred to in the present invention, plus the granulation process to a powder, refers to granules having a particle size 50～5000Myuemu. The tablet referred to in the present invention refers to a tablet obtained by compression-molding a powder or granules into a certain shape. Among the solid processing agents, tablets are preferably used because they have high replenishment accuracy and are easy to handle.

To solidify the photographic processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily formed photographic processing agent. Any means can be adopted, such as forming a coating layer by spraying, for example, JP-A-4-29136 and JP-A-4-29136.
-85535, 4-85536, 4-8553
No. 3, 4-85534, and 4-172341 can be appropriately selected and used.

A preferred tablet production method is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. Compared to a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet, there is an advantage that solubility and storage stability are improved, and as a result, photographic performance is stabilized.

The granulation method for tablet formation is to use a known method such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. Can be done.
Next, the resulting granules when pressure compression known compressor, for example, a hydraulic press machine, a single punch tableting machine, rotary tableting machine, can be used briquetting machine.
The solid processing agent obtained by pressurization and compression can take any shape, but from the viewpoint of productivity, handling properties or dust when used on the user side, cylindrical, so-called tablets are used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component such as an alkali agent, a reducing agent, a bleaching agent, a preservative, and the like.

The method for producing a tablet processing agent is described, for example, in JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
No. 88025, British Patent No. 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-10942 and 2-9042.
Nos. 109043, 3-39735 and 3-397
It can be produced by a general method described in the specification such as No. 39. Further, powder processing agents are described, for example, in JP-A-54-133.
No. 332, British Patent Nos. 725,892 and 729,
It can be produced by a general method as described in each specification such as No. 862 and German Patent No. 3,733,861.

[0097] The solid treating agent exhibits the effects of the present invention more favorably by containing a water-soluble polymer and / or saccharide. It is considered that the water-soluble polymer and / or saccharide is adsorbed on the surface of the silver halide grains in the light-sensitive material and has an effect of stabilizing the concentration of the processing agent near the surface. This effect is particularly remarkable in the case of silver halide grains having dislocation lines. For stable processing, it is effective to use a solid processing agent containing a water-soluble polymer and / or saccharide.

Examples of preferable water-soluble polymers and saccharides that can be used by being contained in the solid processing agent are shown below, but are not limited thereto.

I. Water-soluble polymer polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, polyvinyl acetate, aminoalkyl methacrylate copolymer,
Methacrylic acid-methacrylic acid ester copolymer, methacrylic acid-acrylic acid ester copolymer, methacrylic acid-based betaine polymer, etc. II. Saccharides Monosaccharides such as glucose and galactose, maltose,
Disaccharides such as sucrose and lactose, mannitol,
Sugar alcohols such as sorbitol and erythritol, pullulan, methylcellulose, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate succinate, carboxymethylethylcellulose, dextrins, starch degradation products, etc. particularly preferred compounds among these, polyethylene glycol (weight average molecular weight 2,000～2
000), methacrylic acid-methacrylic acid ester copolymers and methacrylic acid-acrylic acid ester copolymers represented by Osdragit manufactured by Rohm Pharma Co., Ltd., erythritol, maltose, mannitol, Pineflow or Paindex manufactured by Matsutani Chemical Co., Ltd. And methacrylic acid-based betaine-type polymers such as Yuka Former manufactured by Mitsubishi Yuka Co., Ltd.

These water-soluble polymers and / or saccharides may be contained inside the solid processing agent, but are preferably localized at least partially on the surface of the solid processing agent. These water-soluble polymers and / or sugars are
It is preferably from 0.1% to 30%, more preferably from 0.5% to 20%, based on the mass of the solid processing agent.

Solid processing agents include color developers, black-and-white developers,
Although used in photographic processing agents such as bleaching agents, fixing agents, bleach-fixing agents, and stabilizers, the color developing agents have a great effect of the present invention, especially the effect of stabilizing photographic performance.

In addition, black and white developers, color developers, bleaching agents, bleach-fixing agents, and stabilizers can be excluded from the regulation of liquid dangerous substances.

It is within the scope of the present invention that the solid processing agent solidifies only one part of a certain processing agent, but preferably all the components of the processing agent are solidified.

It is preferable that all processing agents to be replenished into each processing tank according to the processing amount information are charged as solid processing agents.
When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishing water.

When the color developing agent is solidified, the alkali agent, the color forming agent and the reducing agent are all converted into a solid processing agent, and in the case of a tablet, at least three agents are most preferably used, and one agent is preferably used. This is a preferred embodiment of the solid processing agent used.

As a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet,
3-137793, 63-97522, Kaikai 1
There are known methods such as -85732, but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is in the form of granules or powders, see JP-A-62-81964 and JP-A-63-8415.
No. 1, Japanese Unexamined Patent Publication No. 1-292375, the gravity drop method described in JP-A-63-105159, and JP-A-63-195345.
Although there is a known method using a screw or a screw described in the number, the present invention is not limited thereto.

The place where the solid processing agent is introduced may be in the processing tank, but is preferably a place where the processing liquid is in communication with the processing section for processing the photosensitive material and the processing liquid flows between the processing section and the processing section. In addition, a structure is preferable in which there is a constant circulation amount of the processing liquid between the processing unit and the dissolved component moves to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

In general, the temperature of an automatic developing machine is controlled by an electric heater, so that the processing solution is controlled by an electric heater. A heat exchange unit is provided in an auxiliary tank connected to a processing tank as a processing unit. Is provided with a pump for feeding the liquid from the processing tank at a constant circulation amount and for keeping the temperature constant.

Usually, a filter is disposed for the purpose of removing foreign substances that are mixed in the processing liquid or generated by crystallization, and play a role of removing foreign substances.

The most preferable method is to put the solid processing agent into a place where the temperature is controlled, such as the auxiliary tank, which is in communication with the processing section. The reason for this is that the insoluble components of the input processing agent are blocked from the processing unit by the filter unit, and the solid content can be prevented from flowing into the processing unit and adhering to the photosensitive material.

In the case where a processing agent charging section is provided in the processing tank together with the processing section, it is preferable to devise a shield or the like so that the insoluble portion does not directly contact the film or the like.

The present invention eliminates the need for a tank or the like for storing a replenisher by charging a solid processing agent into a processing tank, thereby reducing the size of the automatic processing machine or dissolving the solid processing agent when the circulation means is provided. The properties are also very good.

Examples of the color developing agent used in the color developing agent include JP-A-6-208215 [0146] to [0145]
51] can be used. Specific examples of the color developing agent preferably used in the present invention are described in JP-A-4-86674, pp. 7-9 (C).
-1) and the ~ (C-16).

Further, as a preservative, JP-A-6-2082
Compounds represented by general formula (N) described in No. 15 [0159] to [0162] can be used.

[0115] Specific examples of the compound represented by the general formula (N) is JP-A-4-86741 of the 11-12 page described (B
-1) to (B-33) and JP-A-3-33846 No. 4
(1) to (56) described on pages 6 to 6.

The compound represented by the general formula (N) is
Usually, it is used in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like.

Further, in the color developer and the black and white developer used in the present invention, JP-A-6-208215 [016]
6] to [0174], a preservative, a buffer, a development accelerator, and an antifoggant can be used.

It is preferable that a triazinylstilbene-based fluorescent whitening agent is contained in the color developer and the developer used in the present invention from the viewpoint of the effects of the present invention. As such a fluorescent whitening agent, JP-A-6-208215 [017]
6] to [0187], compounds represented by general formula [E] are preferred.

The above compounds can be synthesized by known methods. E-4 of particularly preferably used among the above-exemplified compounds, E-24, E-34, E-35, E-3
6, E-37 and E-41. The amount of these compounds to be added is preferably adjusted to a range of 0.2 g to 10 g per liter of the color developing solution, and more preferably 0.4 g to 5 g.

Further, JP-A-6-208 is used together with a developing agent.
Auxiliary developers, chelating agents and surfactants described in No. 215 [0190] to [0197] can also be used.

The amount of the chelating agent to be added to the solid processing agent is preferably in the range of 0.1 to 20 g per liter of the color developing solution and the black and white developing solution, more preferably in the range of 0.2 to 8 g. It is.

The bleaching agent preferably used for the bleaching agent or the bleach-fixing agent is described in JP-A-6-208215 [0198].
A ferric complex salt of an organic acid according to [0205].

Among the above-mentioned compound examples, those particularly preferably used are (C-1), (C-3), (C-4) and (C-4).
-5) and (C-9), and particularly preferred is (C-1).

It is preferable that the stabilizing solution contains a chelating agent having a chelating stability constant for ferric ion of 8 or more. Here, the chelate stability constant is defined as L.C. G. FIG. S
illen A. E. FIG. Martell, "Stabi
litery Constants of Metal-i
on Complexes ", The Chemical
l Society, London (1964);
Chaberek A. E. FIG. Martell, "Or
Ganic Sequestering Agent
s ", Wiley (1959) and the like.

As a chelating agent having a chelate stability constant of 8 or more with respect to ferric ion, JP-A-3-1827
No. 50 and the like.

The use amount of the above chelating agent is preferably 0.01 to 50 g, more preferably 0.05 to 20 g per liter of the stabilizing solution, and good results can be obtained.

[0127] Further preferred compounds to be added to the stabilizing solution, ammonium compounds. The addition amount of the ammonium compound is stable per liter 0.001.
0 mols, more preferably 0.002 to
It is in the range of 2.0 moles.

The stabilizer preferably contains a sulfite. The stabilizer preferably contains a metal salt in combination with the chelating agent. Such metal salts include B
a, Ca, Ce, Co, In, La, Mn, Ni, B
i, Pb, Sn, Zn, Ti, Zr, Mg, Al or S
r metal salts, halides, hydroxides, sulfates,
It can be supplied as an inorganic salt such as a carbonate, a phosphate, an acetate, or a water-soluble chelating agent. The amount used is preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol per liter of the stabilizer,
More preferably, it is in the range of 4 × 10 ⁻⁴ to 2 × 10 ⁻² mol.

As an automatic developing machine according to the present invention, those described in JP-A-6-208215 [0050] to [0066] can be used.

(Invention according to claim 4) In the invention according to claim 4, after exposing a photosensitive material containing a fluorinated surfactant represented by the general formula (F) to the photosensitive material, It is characterized in that it is processed with a color developing solution containing the compound represented by (a), and is processed with a color developing solution containing a hydroxylamine compound which is excellent as an antioxidant.

That is, by combining a photosensitive material containing a fluorine-containing surfactant represented by the general formula (F) with a process using a color developing solution containing a specific hydroxylamine compound, Further effects are expected compared to the processing with a color developing solution.

In the general formula (a), R ₁ and R ₂ each represent an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and R ₁ and R ₂ each have 1 to 1 carbon atoms represented by R ₁ and R ₂ .
Examples of the alkyl group 3 include those having a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (eg, a chlorine atom, a fluorine atom, a bromine atom, etc.) and an alkenyl group (eg, an allyl group, etc.). R ₁ and R ₂
Specific examples of the alkyl group include a methyl group, an ethyl group, a hydroxyethyl group, an (i) -propyl group, and a propyl group. Examples of the alkoxy group represented by R ₁ and R ₂ include a methoxy group and an ethoxy group. However, R ₁ and R ₂ may combine to form a ring.

R ₁ and R ₂ are preferably both alkyl groups having 1 to 3 carbon atoms, and more preferably both R ₁ and R ₂ are ethyl groups.

Hereinafter, specific examples of the compound represented by the formula (a) will be illustrated, but the present invention is not limited thereto.

[0135]

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These compounds are usually hydrochloride, sulfate, p
Used in the form of salts such as toluenesulphonate, oxalate, phosphate, acetate;

The concentration of the compound represented by the formula (a) in the color developing solution is approximately the same as that of hydroxylamine which is usually used as a preservative, for example, 0.1 g / L to 50 g.
/ L is preferably used, more preferably 0.5 g / L
２０20 g / L.

(Invention according to claim 5) In the invention according to claim 5, after the photosensitive material containing the fluorinated surfactant represented by the general formula (F) is exposed to light, It is characterized in that it is developed with a bleaching solution or a bleach-fixing solution containing at least one selected from the formulas (b) to (e). A bleaching process and a bleach-fixing process, which have rapid desilvering properties, are excellent in recoloring properties, have less bleaching fog, and cause less stain.

In the general formula (b), the alkylene group having 2 to 6 carbon atoms represented by X and the alkylene group having 1 to 5 carbon atoms represented by B ¹ and B ² may be a linear alkylene group. may be a branched alkylene group, also include those having a substituent, examples of the substituent, for example, OH group and the like. In the general formula (e), a divalent aliphatic group represented by X ₁ and X ₂ , a divalent aromatic group or a divalent linking group composed of an aliphatic group and an aromatic group include: Those having a substituent are also included, and examples of the substituent include a carboxyl group and a pyridyl group.

Preferred examples of the compound represented by formula (b) are shown below, but are not limited thereto.

[0141]

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[0142]

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In the above compounds, potassium salts, sodium salts and ammonium salts may be used. Among these, particularly preferred compounds are (b-1), (b-3),
(B-5) and (b-15), and more preferred compounds are (b-1) and (b-3).

The compound represented by the general formula (b) is described in Zh.
Obshch. Khim. , 49, 659 (197
9), Inorganic Chemistry, Vo
l. 7, 2405 (1968), Chem. Zrest
i, 32, 37 (1978); U.S. Pat. No. 3,158,6.
No. 35, JP-A-5-303186 and the like.

Preferred specific examples of the compound represented by formula (c) are shown below, but it should not be construed that the invention is limited thereto.

[0146]

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In the above compounds, potassium salts, sodium salts and ammonium salts may be used. Among these, particularly preferred compounds are (c-1), (c-2),
(C-3).

Preferred specific examples of the compound represented by formula (d) are shown below, but it should not be construed that the invention is limited thereto.

[0149]

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In the above compounds, potassium salts, sodium salts and ammonium salts may be used. Among these, particularly preferred compounds are (d-1), (d-2),
(D-4).

Preferred specific examples of the compound represented by formula (e) are shown below, but it should not be construed that the invention is limited thereto.

[0152]

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[0153]

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In the above compounds, potassium salts, sodium salts and ammonium salts may be used. Among these, particularly preferred compounds are (e-1), (e-2) and (e).
-3) (e-4) and (e-8), more preferably (e-1), (e-2) and (e-4).

The compound represented by the general formula (e) is described in Zh.
Obshch. Khim. , 49, 659 (197
9), and can be synthesized by a generally known method described in JP-A-6-95319.

In the present invention, the effect of the present invention can be obtained by using both a ferric complex salt of the compound represented by the general formula (b) and a ferric complex salt of the compound represented by the general formulas (c) to (e). Can be achieved more favorably.

The compounds represented by the general formula (b) include optical isomers “R, R”, “R, L”, “L, R”, “L,
The "L" form exists. These isomers may or synthesized individually, also be synthesized as a mixture. Among these isomers, “L, L” is required to exert the effect of the present invention more.
It is preferred to use a body.

In the present invention, the compound represented by the general formula (b)
Ferric complex salt concentration of the compound represented by the ferric complex salt concentration and the formula in compound represented by (c) ~ (e),
By adjusting to the range of 0.5 <A / B <9.0,
The effects of the present invention can be further exhibited. Here, A is the concentration (mol / L) of the ferric complex salt of the compound represented by the general formula (b), and B is the concentration of the ferric complex salt of the compound represented by the general formulas (c) to (e). (Mol / L). Further, the concentration of the ferric complex salt of the compound represented by the general formula (b) and the concentration of the ferric complex salt of the compound represented by the general formulas (c) to (e) are set to 1.0 <A / B. By adjusting the content to the range of <5.0, the effect of the present invention can be further exhibited.

In the present invention, the above general formulas (b) to (b)
In the ferric complex salt of the compound represented by (e), the molar ratio of ferric ion to the compound represented by formulas (b) to (e) is in the range of 1: 1 to 1: 3. And more preferably in the range of 1: 1.1 to 1: 2.5.

The processing solution having the bleaching ability may be a bleaching solution for bleaching a silver halide silver image, a bleach-fixing solution having a function of bleaching and fixing a silver halide silver image, and a replenisher thereof. it can.

Next, the case where the processing solution for a silver halide photographic light-sensitive material having the bleaching ability of the present invention is a bleaching solution or a bleach-fixing solution will be described.

The bleaching solution or the bleach-fixing solution contains the compounds represented by the general formulas (b) and (c) to (e) in a total amount of 0.05 to 2.0 mol per liter. Is more preferable, and more preferably it is contained in the range of 0.1 to 1.0 mol.

The bleaching solution and the bleach-fixing solution are described in
-295258 and the compounds represented by the general formulas (b) to (e) described in the publication and at least one of these exemplified compounds have an effect on the speed of treatment. Can play.

In addition to the above accelerators, JP-A-62-1234
No. 59, pp. 51 to 115, JP-A-63-17445, pp. 22 to 25, JP-A-53-95630, JP-A-53-95630.
Compounds described in the respective publications, such as No. 426, can also exert an effect on the rapidity of treatment similarly to the above compounds.

The bleaching solution and the bleach-fixing solution are usually at 20 ° C. to 5 ° C.
Preferably used at 0 ° C, more preferably at 25 ° C
~ 45 ° C.

[0166] The pH of the bleaching solution is preferably set to 6.0 or less, more preferably be 1.0 to 5.5. The pH of the bleach-fixing solution is preferably in the range of 5.0 to 9.0, more preferably 5.5 to 8.0.
5 The pH of the bleaching solution or bleach-fixing solution described above
Is the pH of the processing tank at the time of processing the silver halide light-sensitive material, and does not mean the pH of a so-called replenisher.

[0167] The bleaching solution or bleach-fixing solution, ammonium bromide in addition to the above, potassium bromide, such as a halide sodium bromide, various fluorescent whitening agents, also allowed to contain a defoaming agent or surfactant it can.

When a bleaching solution or a bleach-fixing solution is used in an automatic processor, a replenisher thereof is usually added to the bleaching solution or the bleach-fixing solution. The replenishing amount of the replenisher for the bleaching solution or the replenisher for the bleach-fixing solution is preferably 500 ml or less per m ^{2 of the} silver halide photographic light-sensitive material to be processed.
More preferably, it is in the range of 0 to 400 ml.
Most preferably, it is within the range of 350 ml. The lower the replenishing amount of the bleaching solution or bleach-fixing solution of the present invention, the more remarkable the effect of the present invention is exhibited.

A bleaching solution or a bleach-fixing solution and a replenisher thereof are
In a treatment bath in order to increase its activity, air optionally by treatment replenisher storage tank, or it may be performed blowing oxygen, or a suitable oxidizing agent, e.g., hydrogen peroxide, bromate, Persulfate and the like may be appropriately added.

When the processing solution having the bleaching ability is a bleaching solution, the silver halide photographic light-sensitive material is fixed by a fixing solution containing a fixing agent after bleaching.

As a fixing agent used in a bleach-fixing solution or a fixing solution having a fixing function, thiocyanates and thiosulfates are preferably used. When thiocyanate is used as the fixing agent, the content of thiocyanate is preferably at least 0.1 mol / L, and when processing a color negative film, it is preferably at least 0.5 mol / L.
Particularly preferably, it is at least 1.0 mol / L. When a thiosulfate is used as a fixing agent, the content of the thiosulfate is preferably at least 0.2 mol / L, and when processing a color negative film, it is preferably at least 0.5 mol / L.

The bleach-fixing solution and the fixing solution may contain one or two or more pH buffers consisting of various salts in addition to these fixing agents. Further, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. Further, compounds which are known to be added to a normal bleach-fix solution, such as alkylamines and polyethylene oxides, can be appropriately added.

Incidentally, silver can be recovered from the bleach-fixing solution and the fixing agent by a known method. The bleach-fixing solution has the following general formula [F] described in JP-A-64-295258, page 56.
It is preferable to add the compound represented by the formula (A) and the exemplified compounds, which not only exerts the effects of the present invention better, but also occurs in a processing solution having a fixing ability when processing a small amount of photosensitive material over a long period of time. Another effect is that the amount of sludge to be produced is extremely small. The compound represented by the general formula [FA] described in the publication is disclosed in US Pat. No. 3,335,1.
No. 61 and U.S. Pat. No. 3,260,718. These general formulas [F
The compounds represented by A] may be used alone or in combination of two or more.

When the compound represented by the general formula [FA] is used, 0.1 to 20
Good results are obtained by the addition in the range of 0 g.

The processing time with the bleaching solution can be arbitrarily set, but is preferably 3 minutes and 30 seconds or less, more preferably 5 seconds to 2 minutes and 20 seconds, and more preferably 10 seconds to 1 minute and 20 seconds. It is particularly preferable to set the range. Further, the processing time by the bleach-fixing solution can be arbitrarily set, preferably 4 minutes or less, and more preferably in the range of 10 seconds to 2 minutes 20 seconds.

In a processing solution for a silver halide photographic light-sensitive material having bleaching ability, when the ratio of ammonium ion to all cations is 50 mol% or less, not only the effects of the present invention but also the odor is improved. In order to reduce the amount, it is one of the preferred embodiments of the present invention to set the ratio of ammonium ions to all cations to 50 mol% or less. Further, the proportion of ammonium ions is preferably set to 30 mol% or less, particularly preferably 10 mol% or less.

(Invention according to claim 6) In the invention according to claim 6, after exposing the photosensitive material containing the fluorinated surfactant represented by the general formula (F) to pH 10.
It is characterized by processing with a color developing solution of 5 or more.
Even if the color development processing is performed in H, an effect is obtained in which an increase in fog and a change in gradation are suppressed.

(Invention according to claim 7) In the invention according to claim 7, after the photosensitive material containing the fluorinated surfactant represented by the general formula (F) is exposed, a color development process is performed. As a step, at least a first black-and-white development step, a reversal processing step, a color development processing step, and a reversal type color development processing comprising a bleaching processing, a fixing step, or a bleach-fixing processing, characterized in that the intermediate density range And the gradation stability can be improved.

Examples of the reversal type color development processing for reversal film include E-6 processing solution (trademark) manufactured by Eastman Kodak Co., Ltd., and E-7 formulation disclosed by the company. According to them, the exposed silver halide color light-sensitive material is subjected to first development including a black-and-white developing agent, washing with water, a reversal bath including a fogging agent, a color development bath having a pH of 11 or more, a conditioner, and bleaching for oxidizing developed silver. The treatment is performed in the order of a bath, a fixing bath for removing silver, and a stabilizing bath for stabilizing the dye image with formalin.

(Invention according to claim 8) In the invention according to claim 8, after the photosensitive material containing the fluorinated surfactant represented by the general formula (F) is exposed to light, a color developing process is performed. Is characterized in that the final processing bath contains substantially no aldehyde compound, and exhibits an excellent effect that the stability of the dye image is high even when the processing is performed in a processing bath containing a non-containing aldehyde compound.

The light-sensitive material containing a fluorinated surfactant according to the present invention exhibits excellent image storability even after being processed in a final processing bath substantially free of aldehyde compounds after color development. Here, "contains substantially no aldehyde compound" means that the concentration of the aldehyde compound in the final treatment bath is 1.0 ×
10 ⁻² mol / L or less, preferably 2.0 × 10 ⁻³ mol / L
L, particularly preferably 1.0 × 10 ⁻³ mol / L or less.

The final treatment bath containing substantially no aldehyde compound will be described. The final processing bath improves the stability of the silver halide color light-sensitive material after the development processing, and is also called a stable bath.

It is also possible to process the photographic material with a processing solution having a fixing ability, for example, a fixing solution or a bleach-fixing solution, and then to carry out a stabilizing process without substantially washing with water. The photosensitive material is not limited, such as a negative film, photographic paper, and reversal film, and can be processed using the stabilizer of the present invention.

The stabilizing solution includes organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate, borate, hydrochloride, sulfate, etc.), surfactants , A preservative, a chelating agent, and a metal salt such as Zn, Al, Sn, Ni, and Bi can be added. These compounds may be used in any combination in amounts that are necessary to maintain the pH of the stabilizing bath and do not adversely affect the stability during storage of color photographic images and the occurrence of precipitation. Absent.

The pH value of the stabilizing solution is preferably in the range of 4.0 to 9.0, more preferably 5.5 to 9.0, particularly preferably for the purpose of improving image storability. Is in the range of pH 6.0 to 8.5. Further, it is also preferable that the Ca and Mg ions in the stabilizing solution be 5 ppm or less in order to achieve the above-mentioned effects.

The fungicides preferably used in the stabilizer include hydroxybenzoic acid ester compounds, phenolic compounds,
Thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds,
They are quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds and benzotriazole compounds. Particularly preferred are phenol compounds, thiazole compounds and benzotriazole compounds from the viewpoint of liquid preservability.

Specific examples include 1,2-benzoisothiazolin-3-one, 2-methyl-4-isothiazoline-
3-one, 2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline-3
-One, sodium o-phenylphenol, benzotriazole and the like. The amount of these fungicides to be added to the stabilizer is preferably in the range of 0.001 g to 20 g per liter, and particularly preferably in the range of 0.005 g to 10 g.

The stabilizing solution includes hexamethylenetetramine, a triazine-based compound and an N-methylol compound (dimethylolurea, trimethylolurea, dimethylolguanidine, N-hydroxymethylhydroxyethylamine, trimethylolmelamine) for the purpose of stabilizing image dyes. Etc.) and an aliphatic aldehyde or the like can be used in combination. However, it is preferable that formalin is not substantially contained from the viewpoint of pollution, and this is a preferred embodiment also from the viewpoint of liquid preservation.

The replenishing amount of the stabilizing solution is preferably 1 to 80 times the carry-in amount from the pre-bath per unit area of the photographic material to be processed. In the present invention, the pre-bath components (the bleach-fixing solution or the bleach-fixing solution) in the stabilizing solution are used. Fixer concentration) is 1/100 or less in the last tank of the stabilizing solution tank, and is 1/1 from the viewpoint of low pollution and solution preservation.
00 to 1/100000, preferably 1/200 to 1 /
It is preferable to configure the treatment tank of the stabilization tank so as to have a concentration of 50,000.

The stabilization tank may be composed of a plurality of tanks, and it is preferable for the present invention that the plurality of tanks be two tanks or more and six tanks or less. In the case of two or more tanks, it is particularly preferable to use a counter current method (a method in which the solution is supplied to a post-bath and overflows from a pre-bath) from the viewpoint of low pollution and improvement of image preservation.

The treatment temperature of the treatment with the stabilizing solution is 15 to 60.
C, preferably in the range of 20 to 45C.

(Invention of Claim 10) The photosensitive material according to the present invention is developed and then converted into an electric signal via an image sensor, for example, an image pickup device such as a CCD, and the information of the signal is converted. It is preferable to perform an operation based on the image information and perform image processing on the captured image information. Here, as a process of converting into an electric signal through an image pickup device such as a CCD, not only reading with a film scanner incorporated in a digital automatic developing machine but also reading with a commercially available film scanner may be performed. Alternatively, the image may be taken directly by a commercially available color digital camera. Further, it is preferable that reading is performed separately for the separated image information such as red, green, and blue. In the present invention, following the above reading, the respective color image information of the obtained developed photosensitive material is synthesized, or a calculation is performed based on the signal information read before and after the synthesis of this image to obtain final image information. (These image synthesis and calculation correspond to image processing in the present invention). Examples of the image processing according to the present invention include a sharpening process called unsharp masking for enhancing sharpness of an image, a smoothing process for reducing noise, and a saturation enhancement for increasing saturation. Image quality improvement processing such as processing. Such image processing is
It can be applied to image information to be processed using commercially available (known) application software or the like. or,
The adaptation amount of each image processing, that is, the most preferable correction condition of the image processing is, for example, in the case of using the software, the operator selects the optimum condition on the CRT screen while actually confirming the effect after the image processing. Can be determined. For each of the image processing conditions obtained as described above, a type of image quality processing and its application amount are registered in advance for each type of film and format, and a program is provided so that correction can be automatically performed after scanning with a scanner. It is preferable to attach them as plug-in software or to incorporate them as scanner software functions in advance.

(Constituent factors of silver halide color photographic light-sensitive material) The following will describe each constituent factor of the silver halide color photographic light-sensitive material of the present invention except for the above-mentioned items.

The silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention is disclosed in
No. 6643, No. 61-14630, No. 61-1121
No. 42, No. 62-157024, No. 62-18556
No. 63-92942, No. 63-151618,
No. 63-163451, No. 63-220238, No. 63-31244, Research Discl
Osure (hereinafter simply abbreviated as RD) 38957, I and III, RD40145 XV and the like can be used.

[0195] When constructing a light-sensitive material of the present invention using a silver halide emulsion, the silver halide emulsion, physical ripening,
It is preferable to use those that have been subjected to chemical ripening and spectral sensitization. The additive used in such a process is RD3
Nos. IV and V of 8957 and XV of RD40145.

Known photographic additives which can be used in the present invention are the same as described in RD38957, Item II-X and RD4014.
Those described in the section I-XIII of No. 5 can be used.

A coupler can be contained in each of the red, green and blue light-sensitive silver halide emulsion layers of the silver halide color photographic light-sensitive material of the present invention. It is preferable that the coloring dye formed from the coupler contained in each of these layers has a spectral absorption maximum separated by at least 20 nm. As the coupler, it is preferable to use a cyan coupler, a magenta coupler, and a yellow coupler. As a combination of each emulsion layer and a coupler, a combination of a yellow coupler and a blue photosensitive layer, a combination of a magenta coupler and a green photosensitive layer, a combination of a cyan coupler and a red photosensitive layer are used, but are not limited to these combinations. , And other combinations.

It can be used DIR compound in [0198] the present invention. Specific examples of DIR compounds that can be used include, for example, D-1 to D-34 described in JP-A-4-114153, and these compounds can be preferably used in the present invention.

DIR that can be used in the present invention
Specific examples of the compounds other than those described above include, for example, U.S. Pat. Nos. 4,234,678, 3,227,554, 3,647,291, 3,958,993,
No. 4,419,886, No. 3,933,500
No., JP-A-57-56837, and JP-A-51-13239.
No. 2,072,363, US Pat.
No. 0,266, RD40145, XIV, and the like.

Further, specific examples of the coupler which can be used in the present invention are described in RD40145, section II and the like.

The additive used in the present invention is RD4014
It can be added by the dispersion method described in section VIII of 5, etc.

In the present invention, the aforementioned RD38957
Known supports described in Section XV and the like can be used.

The light-sensitive material of the present invention includes the aforementioned RD3895
Auxiliary layers such as a filter layer and an intermediate layer described in the section 7 XI can be provided.

The light-sensitive material can have various layer structures such as a normal layer, a reverse layer, and a unit structure described in RD38957, section XI.

The silver halide emulsion according to the present invention can be used for various color light-sensitive materials represented by general or movie color negative films, slide or television color reversal films, color papers, color positive films and color reversal papers. Can be preferably applied.

[0206]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Sample 101) On a cellulose triacetate film support having a thickness of 125 μm provided with an undercoat layer, Table 1 was prepared.
Each layer having the composition shown in Table 3 was applied to prepare Sample 101 which is a multilayer color photosensitive material. The plasticizer contained in the cellulose triacetate film support is triphenyl phosphate.

[0208] In all the following examples, the amount of the multilayer color light-sensitive material, in particular shows the number of grams per 1 m ² unless otherwise noted. Silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in moles per mole of silver halide in the layer used.

[0209]

[Table 1]

[0210]

[Table 2]

[0211]

[Table 3]

In addition to the above-mentioned composition, compounds SU-1 and S
U-2, viscosity modifier V-1, stabilizers ST-1, ST-
2. Antifoggants AF-1, AF-2, AF-3, dyes AI-1, AI-2, AI-3, and preservative DI-1 were appropriately added to each layer.

[0213]

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[0214]

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[0215]

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[0216]

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[0219]

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[0218]

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[0219]

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[0220]

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[0221]

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The characteristics of each of the emulsions used for preparing the above samples were
It is shown in Table 4. In addition, the average particle diameter was shown by the particle diameter converted into a sphere.

[0223]

[Table 4]

The silver iodobromide emulsions b, c, d, e, and
f and g are 1 × 10 ^-7mol / 1mo
Contains 1Ag. Further, silver iodobromide b, e, g
Have a dislocation line in the fringe portion of the particles. Iodobromination
Each emulsion except silver emulsion h, after adding the sensitizing dye,
Sodium thiosulfate, chloroauric acid, selenoureas, thiosi
Optimum fog-sensitivity relationship by adding potassium phosphate etc.
Was subjected to chemical sensitization.

The total silver coating amount (silver coating amount in terms of metallic silver) of Sample 101 was 3.65 g / m ² .

(Preparation of Samples 102 to 112) Sample 101
The surfactants SU-3 and SU used in the fourteenth layer
Samples 102 to 112 were prepared in the same manner except that -4 was changed to the fluorinated surfactant according to the present invention described in Table 5. However, when used alone in the table,
0.006 g / m ² , or 0.003 g / m ² when two kinds were used in combination.

[0227]

[Table 5]

(Exposure and Color Development) [Exposure] Samples 101 to 112 produced as described above
Was exposed for 1/200 second using a light source with a color temperature of 5400 ° K. through a wedge-shaped wedge for sensitometry measurement, and then subjected to the following color development processing.

[Color Development Processing] The exposed sample was divided into two parts, and the following color development processing a and color development processing b were performed. The color developing process a is a standard color developing process performed using a color developing solution, a bleaching solution, a fixing solution, a stabilizing solution, and a replenisher, and the color developing process b is a color developing time of the developing process a, a color developing process. This is a development process in which the amount of the main chemical and the pH are changed.

<< Color development processing a: reference development processing >> [Development processing and replenishment conditions] Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 700 ml Bleaching 45 seconds 38 ± 2. 0 ° C. 150 ml Fixing 1 min 30 sec 38 ± 2.0 ° C. 830 ml Stabilizing 60 seconds 38 ± 5.0 ° C. 830 ml drying 1 min 58 ± 5.0 ℃ - * the replenishing amount is a value per photosensitive material 1 m ² is there.

[0231] color developer, bleaching solution, fixing solution, stabilizing solution and the replenisher were used as follows.

[Color developing solution and color developing replenishing solution] Developer replenishing solution Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Potassium iodide 1.2 mg-Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-Developing agent: 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4 5.5 g 6.3 g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, and add potassium hydroxide or 20%
The color developing solution is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18 using sulfuric acid.

[Bleaching Solution and Bleaching Replenisher] Bleaching Solution Replenisher Water 700 ml 700 ml 1,3-diaminopropanetetraacetate ammonium (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g Add 56 g of water to make up to 1 liter, and adjust the pH of the bleaching solution to 4.4 and the pH of the replenishing solution to 4.0 using ammonia water or glacial acetic acid.

[Fixing Solution and Fixing Replenisher] Fixing Solution Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid is used to adjust the pH of the fixing solution to 6.2.
Then, the pH of the replenisher is adjusted to 6.5, and then water is added to make 1 liter.

[Stabilizing Solution and Stabilizing Replenishing Solution] Water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC L-77) 0.1 g ammonia water 0.5 ml After adding water to make 1 liter, ammonia water or 50
Adjust to pH 8.5 with% sulfuric acid.

<< Color Developing Process b: Rapid Developing Process >> In the above color developing process a, the processing time of the color developing process is set to 60 hours.
In a second, the color developing process b was performed in the same manner except that the amount of the developing agent in the color developing solution was changed to 6.3 g and the pH of the color developing solution was changed to 10.20.

(Evaluation of Developed Samples) Each of the developed samples prepared as described above was measured with a transmission densitometer manufactured by X-rite using each of red, green, and blue transmitted light to obtain respective densities. The measurement is performed, and a characteristic curve composed of the horizontal axis—exposure amount (LogE) and the vertical axis—optical density (D) is prepared. Each minimum density (also referred to as Dmin) and minimum density +
Drawing a straight line connecting the density points and density 1.7 0.2, the slope (also called gamma) tan .theta measured, respective differences between the color development processing a color developing process b (.DELTA.Dmin, [Delta] [gamma])
Is obtained, and the obtained results are shown in Table 6. It is to be noted that the smaller the value is, the smaller the performance change between the reference processing and the rapid processing is.

[0238]

[Table 6]

As is clear from Table 6, the sample according to the first aspect of the present invention has a small gradation variation between the standard development processing and the rapid development processing.

Example 2 Using the samples 101 to 112 prepared in Example 1, the color developing agent of the color developing solution in the color developing process a described in Example 1 was changed to the developing agent according to the present invention described in Table 7 Each developed sample was prepared in the same manner except that the sample was changed to.

[0241]

[Table 7]

(Evaluation of Environmental Dependence of Cyan and Magenta Dyes) When printing on color photographic paper using each of the developed samples obtained, the temperature of each sample in the printer was 5 ° C. The environment was set to the case of 40 ° C., the prints were made, and the cyan and magenta component densities were measured on the color print due to the difference in the temperature at the time of printing the sample, and the density difference under both conditions was examined. . The larger the density difference, the lower the color reproducibility of red and green. Table 8 shows the results obtained as described above.

[0243]

[Table 8]

As is clear from Table 8, the sample according to the second aspect of the present invention is hardly affected by the temperature fluctuation of the negative film during printing, and has excellent color reproducibility of the obtained print. .

Example 3 The sample 101 prepared in Example 1 was cut into a standard 135-size 24-shot standard and stored in a film cartridge, and a camera (manufactured by Konica Corporation; Big Mini NE) was used.
O) and a test pattern was photographed. This test pattern is a pattern obtained by statistically processing and averaging the exposure level, color balance, etc. of the scene shot by a general user. It is designed so that the development processing level can be almost reproduced. Also, a commercially available color negative film “Gold 10 manufactured by Eastman Kodak Company”
Similarly, a large number of test patterns were photographed for "0".

(Development processing B) [Preparation of tablet for color development processing] The tablet for color negative film processing used in the present invention was prepared as follows.
Paragraph number [0333] of JP-A-2000-284430
According to the procedures (1) to (10) described in [0343], tablets for replenishing color development for color negatives, tablets for replenishing bleaching for color negatives, tablets for fixing and replenishing color negatives, and tablets for stable replenishing for color negatives were produced.

[Color Negative Processing Step] Next, a method for processing a photosensitive material using the automatic developing machine according to the present invention will be described below.

Konica Color Negative Film Processor C
A tablet supply function, a liquid level detection function, a hot water supply function, and the like were installed in the L-KP-50QA by modification, and the following processing experiments were performed. The standard processing conditions are shown below.

Processing Step Temperature Time Color Development 38 ± 0.3 ° C. 3 minutes 15 seconds Bleaching 38 ± 1.0 ° C. 45 seconds Fixing-1 38 ± 1.0 ° C. 45 seconds Fixing-2 38 ± 1.0 ° C. 45 seconds Stable-1 38 ± 3.0 ° C 20 seconds Stable-2 38 ± 3.0 ° C 20 seconds Stable-3 38 ± 3.0 ° C 20 seconds Drying 60 ° C 60 seconds The stabilizer is the third tank (stable -3)
In the tank (stability-2) and the first tank (stability-1), the fixing agent is replenished in the second tank (fixing-2) and the overflow liquid flows into the first tank (fixing-1). .

Each processing solution was prepared according to the following formulation, and the temperature was adjusted. << Color developing tank liquid >> (per liter) Potassium carbonate 30.0 g Potassium bicarbonate 4.2 g Sodium sulfite 4.5 g Diethylenetriaminepentasodium pentasodium 2.6 g Polyethylene glycol # 6000 (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.0 g Sodium p-toluenesulfonate 3.0 g Mannit 3.0 g Hydroxylamine sulfate 4.0 g Potassium bromide 1.7 g Potassium iodide 4 mg Disodium pyrocatechol-3,5-disulfonate 0.2 g Pine flow (Matsuya Chemical Co., Ltd.) 0.32 g CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] 5.0 g sodium N-myristoylalanine 0.3 g pH = 10 with sulfuric acid or potassium hydroxide 0.0 ± 0.05.

<< Bleaching Solution >> (per liter) 1,3-propanediaminetetraacetic acid ferric ammonium monohydrate 140.0 g 1,3-propanediaminetetraacetic acid 6.7 g potassium bromide 60.0 g succinic acid 70 2.0 g disodium succinate hexahydrate 28.1 g mannitol 14.0 g Demol MS (manufactured by Kao Corporation) 2.1 g β-cyclodextrin 3.5 g N-lauroyl sarcosine sodium 7.2 g pH = 4 with potassium carbonate 0.35 ± 0.5.

<< Fixing solution >> (per liter) Ammonium thiosulfate 225.0 g Sodium thiosulfate 25.0 g Sodium sulfite 18.0 g Ethylenediaminetetraacetate disodium 3.5 g Pine flow (Matsuya Chemical) 10.0 g N-lauroyl sarcosine Sodium 1.5g Adjust pH = 7.0 ± 0.5 with potassium carbonate.

<< Stabilizing Solution >> (per liter) m-hydroxybenzaldehyde 1.5 g Megafac F116 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 g lithium hydroxide monohydrate 0.16 g disodium ethylenediaminetetraacetate 0 0.2 g Pine Flow (Matsuya Chemical) 0.1 g Adjust pH = 8.5 ± 0.5 with potassium hydroxide.

During the temperature control of each processing tank, 20 refill tablets were set in the refill tablet supply device. These refill tablets are refilled into the processing tank in accordance with the number of processed 135-size, 24-shot films. One tablet for color development replenishment is added every time 7.5 films are processed, one tablet for bleach replenishment is added to five films, and one tablet for fixation replenishment is added to one film, and hot water is supplied at the same time. Each time two films of replenished hot water are processed from the device,
40.0 ml for the color developing tank and 10.0 m for the bleaching tank
1 and 60.0 ml to the fixing tank and 70 ml to the stabilizing tank.

Two lines of the above-mentioned development processing lines were prepared, and a sample 101 that had been subjected to one round of running processing was subjected to development processing line A, a commercially available color film (Gold 1).
00), a line subjected to one round of running processing was designated as a development processing line B. In the present invention, one round refers to a point in time when each processing solution is replenished in accordance with the number of samples to be processed and the total amount of the replenishing solution reaches the processing tank capacity.

Next, the samples 101 to 101 produced in Example 1
Similarly, the sample was cut into 135 size, loaded into a camera, photographed with a sensitometric panel, and then developed in the two lines of solid processing agent type development processing lines A and B, and each sample was processed. Was measured by the following method.

Tones γB, G, R: slope of line segment connecting density point of minimum density + 0.3 and density point of minimum density + 1.8 in characteristic curve prepared in the same manner as in Example 1. I asked.

Tone difference Δγ B, G, R: development processing line A
The absolute value of the difference between the gradations γB, G, and R in the above and the gradations γB, G, and R in the development processing line B was obtained.

Table 9 shows the results obtained as described above.

[0260]

[Table 9]

As is clear from Table 9, according to the processing method of the third aspect of the present invention, when processing was carried out using a developing solution of a solid processing agent replenishing type, fluctuations between developing stations were reduced. ,
It can be seen that it is hardly affected by the influence and the reproducibility is excellent.

Example 4 In Example 1, the color developing solution used in the color developing process a was used as a color developing solution 8, and then the hydroxylamine sulfate used in the color developing solution 8 was replaced with the same compound (1) of the same mass. ,
Color developing solutions 9, 10, and 11 were prepared in the same manner except that (3) and (5) were used.

[0263] The color developing solution 8-11 and left for one week to stir weakly while keeping each 38 ° C., and a color developer 8'～11 '. Samples 101 to 101 produced in Example 1
112 was exposed to sensitometry measurement in the same manner as in Example 1, and the color developing solutions 8 to 11 (reference processing) and 8 'to 11' (forcible deterioration processing) were used. The described color development processing a was performed.

The density of each of the developed samples prepared as described above was measured by the method described in Example 1, and the increase in the magenta and cyan fog densities (GΔDmin, RΔDmi
n) was measured, and the results obtained are shown in Table 10.

[0265]

[Table 10]

As is clear from Table 10, the developing solution according to the fourth aspect of the present invention is less susceptible to an increase in fog due to the forced deterioration treatment. Due to the synergistic effect with the preservative, excellent storage stability of the color developing solution could be confirmed.

Example 5 In the color developing treatment using the color developing solution 8 described in the above Example 4, instead of the ethylenediaminetetrairon ammonium acetate compound in the reference bleaching solution, the exemplified compound b-
3, the iron ammonium salt of each of the exemplified compound c-4, the exemplified compound d-2, and the exemplified compound e-6 was 0.32 mol /
L, and bleaching solutions 1, 2, 3, 4
Was prepared.

Samples 101 to 112 produced in Example 1
Was subjected to sensitometric measurement exposure in the same manner as in Example 1, and in the color development processing a described in Example 1,
Only the bleaching solution was changed to the above-described bleaching solutions 1 to 4, and color development processing was performed, and the color reproducibility of the cyan image and the processing stain were measured.

(Evaluation of Reproducibility of Cyan Image)
The red light density value C (DL) of the sample after the color development processing at the maximum exposure part (Dmax part) was measured, and the measured sample was then used as a 0.2 mol / L solution of an ethylenediaminetetrairon ammonium iron compound (pH 6). .0) for 5 minutes, after immersion, washing with water and drying, measuring the red light density value C (RC) again,
The recolorability ΔC = C (DL) −C (RC) was determined. If the recoloring property is poor, the negative value increases.

(Evaluation of Treated Stain) The surface of each developed sample was visually observed, and the ratio of stain on the surface having the photosensitive layer was evaluated according to the following criteria.

A: less than 1% B: 1% or more to less than 10% C: 10% or more to less than 50% D: 50% to less than 100%

In the above-mentioned evaluation ranks, it was judged that if the rank was equal to or higher than the rank B, there was no practical problem.

Table 11 shows the results obtained as described above.

[0274]

[Table 11]

As is clear from Table 11, under the processing conditions according to claim 4 of the present invention, even if the bleaching processing solution having a lower concentration is used, the bleaching processing solution has a lower concentration in relation to the iron chelate compound in the bleaching processing solution. It can be seen that the color properties are excellent and the film stain is small.

Example 6 The same as the color developing process a except that the color developing process a and the color developing solution 8 described in Example 5 were used to adjust the pH to 10.7 and the color developing time to 2 minutes. Under the two conditions, the samples 101 to 112 prepared in Example 1 were subjected to sensitometric measurement exposure, then subjected to color development, and evaluated for gradation stability in high pH short-time development. did.

(Gradation Stability) The difference Δγ between the gradations γa of the magenta (G) and cyan (R) densities in the color development processing a and the gradations γa in the high pH and short time development processing,
γa-γs was measured. The smaller the value is, the closer to 0, the better the gradation stability.

Table 12 shows the results obtained as described above.

[0279]

[Table 12]

As is clear from Table 12, the constitution according to claim 6 of the present invention is excellent in that it is hardly affected by the fluctuation in gradation stability in high pH short-time development processing, and is excellent. I understand.

Example 7 (Preparation of Sample 701) Table 13 and Table 1 were placed on a 125 μm-thick cellulose triacetate film which had been subjected to a subbing process.
Each layer described in No. 4 was sequentially coated from the support side to prepare a reversible silver halide color photographic material sample 701.

The coating amount of each component in the table is shown in g / m ² . However, with respect to silver halide, it is indicated by a coating amount converted to silver.

[0283]

[Table 13]

[0284]

[Table 14]

In each layer in the table, in addition to the above composition, gelatin hardeners H-1 and H-2, a surfactant, and a preservative DI-
1 (0.56 mg / g of gelatin) was added.

Each emulsion was desalted and washed with water, and then subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to give a sensitizing dye and a stabilizer (4).
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene) and an antifoggant (1-phenyl-5-mercaptotetrazole).

The structure of the composition used for the above sample is as follows. AS-1: 2,5-di-t-octylhydroquinone H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium SA-1: di (2,2,3,3, sulfosuccinate) 4,4,4
5,5,6,6,7,7-dodecylfluoroheptyl)
Sodium O-1: di (2-ethylhexyl) phthalate O-2: dibutyl phthalate O-3: tricresyl phosphate

[0288]

Embedded image

[0289]

Embedded image

[0290]

Embedded image

Table 15 shows the photosensitive silver halide emulsions used for preparing the above samples.

[0292]

[Table 15]

(Preparation of Samples 702 to 712) The surfactant (SA-
In place of 1), as shown in Table 16, 102 of Example 1
Samples 702 to 712 were produced in the same manner except that the same fluorinated surfactant as that used in Nos. To 112 was used.

(Exposure and reversal development processing) After exposing each sample to a sensitometric measurement exposure, the following reference reversal development processing was performed and the processing time of the first development was changed to 8 minutes in the same manner. A sensitized development process was performed.

<Processing Step A> Processing Step Processing Time Processing Temperature First Development 6 minutes 38 ° C. Rinse 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color Development 6 minutes 38 ° C. Adjustment 2 minutes 38 ° C. Bleaching 6 minutes 38 C. Fixation 4 minutes 38.degree. C. Washing with water 4 minutes 38.degree. C. Stabilization 1 minute Room temperature drying The composition of the processing solution used in the above-mentioned processing step A is as follows.

<First developer> Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2 0.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added to make up to 1000 ml. (PH 9.60) <Inversion liquid> Nitrilotrimethylenephosphonic acid hexasodium salt 3 g Stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to make up to 1000 ml. (PH 5.75) <Color developing solution> Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium tertiary phosphate (dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazinic acid 1. 5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1 g Water was added to make up to 1000 ml. (PH 11.70) <Conditioner> Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water was added to make up to 1000 ml. (PH 6.15) <Bleaching liquid> Sodium ethylenediaminetetraacetate (dihydrate) 2 g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) 120 g Ammonium bromide 100 g Water was added to make up to 1000 ml. (PH 5.56) <Fixing solution> Ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5 g Water was added to make up to 1000 ml. (PH6.60) finished with 1000ml added <stabilizing solution> Formalin (37 wt%) 5 ml Konidakkusu (manufactured by Konica (Ltd.)) 5 ml water. (PH 7.00) Tones γR, γG, and γB obtained by measuring red, green, and blue light densities in the reference reversal development process, whereas gradations γRA, γGA obtained by measuring red, green, and blue light densities in the sensitized reversal development process ,
γBA was measured and the respective differences ΔγRA-R, ΔγGA
-G and ΔγBA-B were measured, and the obtained results are shown in Table 16.

[0297]

[Table 16]

As is apparent from Table 16, according to the embodiment corresponding to the seventh aspect of the present invention, the sample having the constitution of the present invention was subjected to sensitizing development processing of a reversal type silver halide color photographic light-sensitive material. It can be seen that the gradation stability is hardly affected by the fluctuation and is excellent.

Example 8 Samples 701 to 712 of the reversible silver halide color photographic light-sensitive material prepared in Example 7 were subjected to sensitometric measurement exposure, and then subjected to the standard reversal developing treatment described in Example 7. Samples 701 'to 712', which were developed by the same reversal development process except that formalin was removed from the stabilized sample and 5.0 g / L of hexamethylenetetramine was added to the conditioning bath (conditioner), and Produced.

After leaving each sample for one week in a dark room atmosphere at 40 ° C. and a relative humidity of 55%, the occurrence of Y stain (increase in the minimum density of Y) and the processing stain were measured. It is shown in Table 17.

[0301]

[Table 17]

As is clear from Table 17, the samples which had been subjected to the color development treatment with the constitution according to the eighth aspect of the present invention exhibited stable dye image stability even when treated in a final treatment bath substantially containing no aldehyde compound. It turns out that it is excellent in property.

Example 9 Three types of LED light sources (manufacturer: maximum peak wavelength, Stanley R: 63) were used for the samples 101 to 112 which had been subjected to the color development processing using the development processing number 1 of the embodiment 2.
5 nm, Nichia Chemical G: 535 nm, Nichia Chemical B: 470 nm) while sequentially switching the R,
The G, B color separation negative image information is converted to a monochrome CCD of 2048 × 2048 pixels (KX manufactured by Eastman Kodak Company).
It read using 4).

Then, after applying the gradation inversion process to the obtained three color separation negative images of each sample, each color separation information of R, G, and B is converted into one by using Photoshop made by Adobe.
A process of combining the two image data was performed to obtain an RGB combined positive image. From these image data, L-size color print samples were prepared using Konica Digital Minilab System QD-21 and Konica Color Paper Type QAA7, and the color shift of prints relating to reproducibility and image defects were evaluated. As a result of the evaluation, in the present invention, there was a tendency that the color reproducibility was excellent, and that image defects considered to be caused by errors when reading the negative film tended to be small.

[0305]

According to the present invention, there is no increase in fog and no deterioration in color density and gradation balance due to each development processing change, excellent color tone of color dye and image stability, and improved desilvering property and processing stain. An image forming method of the obtained silver halide color photographic light-sensitive material and an image information forming method using the same can be provided.

────────────────────────────────────────────────── ─── of the front page continued (51) Int.Cl. ⁷ identification mark FI theme Court Bu (reference) G03C 7/413 G03C 7/413 7/42 7/42 7/44 7/44

Claims (10)

[Claims] 1. A silver halide color photographic material having a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on one side of a support is exposed to light and then developed. In an image forming method for obtaining a dye image by developing, at least one layer of the silver halide color photographic light-sensitive material contains a compound represented by the following general formula (F), and is used in the color developing process. An image forming method for a silver halide color photographic light-sensitive material, wherein the processing time of the step is 95 to 120 seconds. Formula (F) Rf- in _{(O-Rf ') n -L} -X m [wherein, Rf represents an alkyl group, an aryl group or an alkenyl group containing at least one fluorine atom, R
f ′ represents an alkylene group containing at least one fluorine atom, L represents a simple bond or a linking group,
Represents a hydroxy group, an anionic group or a cationic group. n and m each represent an integer of 1 or more. ] 2. A silver halide color photographic light-sensitive material having a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on one side of a support is exposed to light. In an image forming method for obtaining a dye image by developing, at least one layer of the silver halide color photographic light-sensitive material contains a compound represented by the formula (F), and the color developing used in the color developing is performed. liquid is an image forming method for silver halide color photographic light-sensitive material characterized by containing a color developing agent at least one selected from the following formulas (1) to (7). Embedded image [Wherein, R _{1 to} R ₆ may be the same or different and each represents a hydrogen atom or a substituent. R ₇ represents an alkyl group.
R ₈ represents a substituent. m represents an integer of 0 to 3. [Chemical formula 2] [Wherein, R ₇ has the same meaning as in formula (1). R _{9 to} R
₁₂ may be the same or different and each represents a hydrogen atom or a substituent. R ₁₃ represents a substituent. n represents the integer of 0-3. [Chemical formula 3] Wherein, R ₁₄ to R ₂₁ may be the same or different, each represents a hydrogen atom or a substituent. R ₂₂ represents a substituent. p
Represents an integer of 0 to 4. [Formula 4] [Wherein, R ₂₃ represents a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 2 to 6 carbon atoms whose main chain has 2 to 6 carbon atoms. Represent. R ₂₄ represents a straight-chain having 2 to 6 carbon atoms or a branched unsubstituted alkylene group having a main chain having 2 to 6 carbon atoms, and a straight-chain having 3 to 6 carbon atoms having a main chain having 2 to 6 carbon atoms. Alternatively, it represents a branched hydroxyalkylene group. R ₂₅ is a straight chain having 1 to 4 carbon atoms;
Represents a branched or cyclic alkyl group. However, this excludes the case where R ₂₃ is an ethyl group, R ₂₄ is an ethylene group, and R ₂₅ is a methyl group. [Chemical formula 5] [In the formula, R ₂₆ represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ₂₇ represents a linear or branched alkylene group having 2 to 6 carbon atoms in which the main chain has 2 to 6 carbon atoms. R
₂₈ represents a linear or branched alkyl group having 1 to 4 carbon atoms.
R ₂₉ represents a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. Provided that R ₂₆ is an ethyl group, R ₂₇ is an ethylene group, R
Except when ₂₈ is a methyl group and R ₂₉ is a methyl group. [Formula 6] [In the formula, R ₃₀ represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ₃₁ is a main chain represents a straight-chain or branched alkylene group having 2 to 6 carbon atoms is 2 to 6 carbon atoms. R
₃₂ and R ₃₃ may be the same or different and have 1 to 1 carbon atoms.
4 represents a linear or branched alkyl group. R ₃₄ has 1 carbon atom
Represents a straight-chain, branched or cyclic alkyl group, a halogen atom, a nitrogen atom or an oxygen atom. q represents an integer of 0 to 4. When q is 2 or more, R ₃₄ may be the same or different. [Formula 7] [Wherein, R ₃₅ represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms. R ₃₆ represents a straight or branched alkylene group having 2 to 6 carbon atoms in which the main chain has 2 to 6 carbon atoms. R
₃₇ represents a hydrogen atom, an alkyl group or a substituent. r is 0
Represents an integer of 1 to 4. When r is 2 or more, R ₃₈ may be the same or different. X is -CO-NR ₃₉ (R ₄₁ ), -C
O-OR _40, and a group selected from the group consisting of _{-SO 2 -NR 39 (R 41)} . At this time, R ₃₉ and R ₄₁ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. R ₄₀ represents an alkyl group or an aryl group. ] 3. A silver halide color photographic material having a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on one side of a support is exposed to light and then developed. In an image forming method for obtaining a dye image by development processing, at least one layer of the silver halide color photographic light-sensitive material contains the compound represented by the formula (F), and is used in the color development processing. An image forming method for a silver halide color photographic light-sensitive material, wherein the liquid is replenished from a replenisher prepared with a solid processing agent. 4. A silver halide color photographic light-sensitive material having a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on one side of a support, followed by color formation. In an image forming method for obtaining a dye image by development processing, at least one layer of the silver halide color photographic light-sensitive material contains the compound represented by the formula (F), and is used in the color development processing. A method for forming an image of a silver halide color photographic light-sensitive material, wherein the liquid contains a compound represented by the following general formula (a). Formula (a) R ₁ —NR ₂ —OH wherein R ₁ and R ₂ each represent an alkyl group or an alkoxy group having 1 to 3 carbon atoms. However, R ₁ and R ₂ may combine to form a ring. ] 5. On one side of the support, a red-sensitive layer, a green
Halogen having a photosensitive layer, a blue photosensitive layer and a non-photosensitive layer
After exposing the silver halide color photographic material, the color developing process
An image forming method for obtaining a dye image by treating
At least one layer of silver halide color photographic light-sensitive material
Containing a compound represented by the formula (F),
Bleaching solution and bleach-fixing solution used in
One is selected from the following general formulas (b) to (e).
Silver halide characterized by containing both
-An image forming method for a photographic light-sensitive material. Embedded image[Where A¹~ A^FourIs -CH_TwoOH, -PO
_Three(M)_TwoOr -COOM, each being the same and
May also be different. M forms a hydrogen atom or a salt
Represents an atom. X is an alkylene group having 2 to 6 carbon atoms or-
(B¹O)_n-B^TwoRepresents-. n represents an integer of 1 to 8,
B¹And B^TwoRepresents an alkylene group having 1 to 5 carbon atoms.
However, they may be the same or different. Embedded image[In the formula, n1 represents 1 or 2, and A represents -COOM.^Three, −
OH, -NH_TwoOr -PO _Three(M^Three)_TwoRepresents M¹, M^Two,
M^ThreeRepresents a hydrogen atom or a salt-forming atom, respectively.
You. ][Wherein, n2 and n3 each represent 1 or 2, and B is water
Represents an element atom or an alkyl group having 1 to 3 carbon atoms. M^Four, M_Five
Represents a hydrogen atom or an atom forming a salt, respectively. Embedded image[Where A^Five, A⁶Is -COOM⁷, -PO_Three(M
⁷)_Two, -SO_ThreeM⁷, A hydroxyl group or a mercapto group
And may be the same or different. M
⁶, M⁷Represents a hydrogen atom or a salt-forming atom, respectively.
You. R represents a hydrogen atom, an aliphatic group or an aromatic group,
X₁, X_TwoAre divalent aliphatic groups, divalent aromatic groups or
Represents a divalent linking group consisting of an aliphatic group and an aromatic group.
You. ] 6. A silver halide color photographic light-sensitive material having a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on one side of a support, followed by color formation. In an image forming method for obtaining a dye image by development processing, at least one layer of the silver halide color photographic light-sensitive material contains the compound represented by the formula (F), and is used in the color development processing. An image forming method for a silver halide color photographic light-sensitive material, wherein the pH of the liquid is 10.5 or more. 7. A silver halide color photographic material having a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on one side of a support is exposed to light and then developed. In an image forming method for obtaining a dye image by developing, at least one layer of the silver halide color photographic light-sensitive material contains a compound represented by the general formula (F), and the color developing is performed by at least Image formation of a silver halide color photographic light-sensitive material, which is a reversal type color development process comprising a black-and-white development process, a reversal process, a color development process, a bleach process, a fixing process or a bleach-fix process Method. 8. A silver halide color photographic light-sensitive material having a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer on one side of a support, and then color-forming. In an image forming method for obtaining a dye image by developing, at least one layer of the silver halide color photographic light-sensitive material contains the compound represented by the formula (F), and the final processing bath of the color developing process Is substantially free of an aldehyde compound. 9. A compound represented by the general formula (F):
The method for forming an image of a silver halide color photographic light-sensitive material according to any one of claims 1 to 8, wherein the image is contained in the outermost layer of the silver halide color photographic light-sensitive material. 10. After forming an image by the method according to claim 1, the formed image information is read by an image sensor, the image information is converted into electric signal information, and based on the electric signal information. Performing image processing by arithmetic processing.